Olefin (co)polymerization where the olefins contain certain functional groups such as silyl may be carried out using certain transition metal compounds as catalysts. Olefins containing other functional groups such as ester or alkenyl may be similarly polymerized and/or the polymerization improved if the olefin contains a xe2x80x9cblocking groupxe2x80x9d such as a quaternary carbon atom.
Polyolefins are useful in many areas as, for example, molding resins for toys and automotive parts, resins for film in packaging, elastomers and other uses. Many times it is desirable to copolymerize an olefin containing one or more functional groups, which may serve to later help crosslink the polymer, change the surface or other physical properties of the polymer, etc. Many olefins may be polymerized by using various transition metal compounds as polymerization catalysts, such as Ziegler-Natta or metallocene-type catalysts. However many times these polymerizations either won""t proceed or proceed poorly in the presence of olefins containing functional groups.
Olefins may also be polymerized using catalysts containing late transition metals such as palladium or nickel, and sometimes functionalized olefins may be copolymerized. However, the range of useful functionalized olefins is limited, and often the efficiency of the polymerization is reduced in the presence of these olefins. Therefore more versatile and/or more efficient polymerizations of functionalized olefins are desired.
World Patent Applications 96/23010 and 97/02298 describe the polymerization of olefins, some of them containing functional groups, using certain transition metal containing compounds. The use of olefins containing blocking groups is not described in these applications.
This invention concerns a process for the polymerization of olefins, comprising, contacting a first olefin selected from the group consisting of cyclopentene, norbornene, and a compound of the formula R1CHxe2x95x90CHR1, a second olefin containing one or more of the functional groups selected from the group consisting of xe2x80x94SiR23, xe2x80x94CO2R3, a nonconjugated ketone, xe2x80x94SO2R7, alkenyl, xe2x80x94C(O)xe2x80x94Oxe2x80x94C(O)R4, xe2x80x94C6F5, xe2x80x94OR8, xe2x80x94CO2H, xe2x80x94OH, xe2x80x94CHO, xe2x80x94OP(O)(OR5)2, xe2x80x94BR62, xe2x80x94SR9, xe2x80x94SH, ether, epoxy, and xe2x80x94CONR68R69, and a nickel or palladium coordination compound of 
Ar1Zp xe2x80x83xe2x80x83(VIII); 
R31R32Nxe2x80x94CR33R34(CR35R36)mxe2x80x94NR31R32 xe2x80x83xe2x80x83(IX); 
xe2x80x83wherein:
Ar1 is an aromatic moiety with n free valencies, or diphenylmethyl;
each Z is xe2x80x94NR52R53 or xe2x80x94CR54xe2x95x90NR55;
p is 1 or 2;
E is 2-thienyl or 2-furyl;
each R52 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
each R54 is independently hydrogen or hydrocarbyl; and
each R55 is independently a monovalent aromatic moiety;
m is 1, 2 or 3;
R53 is hydrogen or alkyl;
each R33, R34, R35 and R36 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R31 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon toms;
each R32 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar2 is an aryl moiety;
R38, R39, and R40 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R37 and R41 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose Es is about xe2x88x920.4 or less;
each R42 and R43 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
Ar3 is an aryl moiety;
R45 and R46 are each independently hydrogen or hydrocarbyl;
Ar4 is an aryl moiety;
Ar5 and Ar6 are each independently hydrocarbyl;
Ar7 and Ar8 are each independently an aryl moiety;
Ar9 and Ar10 are each independently an aryl moiety or xe2x80x94CO2R56, wherein R56 is alkyl containing 1 to carbon atoms;
Ar11 is an aryl moiety;
R50 is hydrogen or hydrocarbyl;
R51 is hydrocarbyl or xe2x80x94C(O)xe2x80x94NR50xe2x80x94Ar11;
R44 is aryl;
R47 and R48 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms;
R49 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety;
R13 and R16 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R14 and R15 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R14 and R15 taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring;
R18 is hydrocarbyl or substituted hydrocarbyl, and R20 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R18 and R20 taken together form a ring;
R19 is hydrocarbyl or substituted hydrocarbyl, and R21 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R19 and R21 taken together form a ring;
each R17 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R17 taken together form a ring;
R27 and R30 are independently hydrocarbyl or substituted hydrocarbyl;
R28 and R29 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and
n is 2 or 3;
which is an olefin polymerization catalyst, and wherein:
each R1 is independently hydrogen or alkyl;
each R2 is independently hydrocarbyl, substituted hydrocarbyl, halogen, acyloxy, amino, siloxy, or xe2x80x94OR12;
R3 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R4 is hydrocarbyl or substituted hydrocarbyl;
each R5 is independently hydrocarbyl or substituted hydrocarbyl;
R6 is hydrocarbyl or substituted hydrocarbyl;
R7 is hydrocarbyl or substituted hydrocarbyl;
R8 is hydrocarbyl or substituted hydrocarbyl;
R9 is hydrocarbyl or substituted hydrocarbyl;
R12 is hydrocarbyl or substituted hydrocarbyl; and
R68 and R69 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
xe2x80x83and provided that:
when said functional group is alkenyl, xe2x80x94OR8, xe2x80x94OH, xe2x80x94CHO, xe2x80x94OP(O)(OR5)2, xe2x80x94SR9, xe2x80x94SH, ether, epoxy, or xe2x80x94CONR68R69 there is a blocking group between a carbon-carbon double bond of said olefin containing one or more of the functional groups and said functional groups; and
when said functional group is a nonconjugated ketone, alkenyl, xe2x80x94C(O)xe2x80x94Oxe2x80x94C(O)R4, xe2x80x94CO2H, xe2x80x94OH, xe2x80x94CHO, xe2x80x94OP(O)(OR5)2, xe2x80x94SR9, or xe2x80x94SH, epoxy, said coordination compound is preferably a palladium compound.
Also disclosed herein is a compound of the formula
H2Cxe2x95x90CHxe2x80x94Txe2x80x94NR71C(O)CFR72(OCF2CFR72)aOCF2(CFR72)bSO2F, xe2x80x83xe2x80x83(XXVI),
wherein:
T is alkylene or substituted alkylene;
R71 is hydrocarbyl or substituted hydrocarbyl;
each R72 is independently fluorine, chlorine or perfluoroalkyl containing 1 to 10 carbon atoms;
a is 0, 1 or 2; and
b is 0 or an integer of 1 to 6.
Also disclosed herein is a copolymer comprising repeat units of the formula 
wherein:
T is alkylene or substituted alkylene;
R71 is hydrocarbyl or substituted hydrocarbyl;
each R72 is independently fluorine, chlorine or perfluoroalkyl containing 1 to 10 carbon atoms;
a is 0, 1 or 2;
b is 0 or an integer of 1 to 6;
R73 is alkyl or hydrogen; and
R74 is hydroxyl, fluorine, chlorine, or OM,
xe2x80x83wherein M is a metal cation.